US4915623A - Calcination apparatus - Google Patents
Calcination apparatus Download PDFInfo
- Publication number
- US4915623A US4915623A US07/317,179 US31717989A US4915623A US 4915623 A US4915623 A US 4915623A US 31717989 A US31717989 A US 31717989A US 4915623 A US4915623 A US 4915623A
- Authority
- US
- United States
- Prior art keywords
- tubes
- kettle
- gases
- gypsum
- combustion chamber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000001354 calcination Methods 0.000 title claims abstract description 16
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 35
- 239000010440 gypsum Substances 0.000 claims abstract description 35
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 37
- 238000002485 combustion reaction Methods 0.000 claims description 23
- 239000000446 fuel Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 238000005243 fluidization Methods 0.000 claims description 4
- 229910052925 anhydrite Inorganic materials 0.000 claims description 3
- 239000003779 heat-resistant material Substances 0.000 claims description 2
- 239000011505 plaster Substances 0.000 claims description 2
- 239000000567 combustion gas Substances 0.000 claims 5
- 238000007599 discharging Methods 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 7
- 239000011507 gypsum plaster Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- 239000001175 calcium sulphate Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
- B01J6/001—Calcining
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B11/00—Calcium sulfate cements
- C04B11/02—Methods and apparatus for dehydrating gypsum
- C04B11/028—Devices therefor characterised by the type of calcining devices used therefor or by the type of hemihydrate obtained
- C04B11/0281—Kettles; Marmites; Autoclaves
Definitions
- This invention relates to calcination apparatus, and more particularly to apparatus for calcining calcium sulphate dihydrate, or gypsum.
- a commercially important method of calcining gypsum is by indirect heating of a bed of gypsum in a calcining kettle.
- the heat input may be enhanced by the direct introduction of hot gas through a dip tube extending downwardly into the bed of gypsum in the kettle.
- Such a method which may be operated as a continuous process, is described in GB 1 488 665.
- the need for indirect heating can be avoided by the use of a conical kettle in which the only source of heating is hot gas passed into the gypsum through a tube to fluidise and calcine it.
- the interior of the kettle is shaped to ensure that all the gypsum in the kettle is calcined.
- a kettle which is particularly suited to continuous operation, is described in GB 2 043 219.
- Direct heating techniques although increasing the throughput of calcining kettles, can lead to the formation of insoluble calcium sulphate anhydrite, which reduce the quality of the plaster produced. It is believed that the temperature of the hot gas entering the gypsum bed is an important factor in the production of anhydrite. The production of insoluble anhydrite occurs when using direct heating fired by gas or oil, but is more marked in the case of gas.
- a method of calcining gypsum comprising contacting the gypsm with non-reactive hot gas from a hot gas source, in which the hot gas is passed into the gypsum from the source through a plurality of tubes extending downwardly into the gypsum.
- apparatus for calcining gypsum comprising a calcining kettle for containing material to be calcined and a plurality of tubes extending generally downwardly into the interior of the kettle, the upper regions of the tubes being in communication with a common source of non-reactive hot gas and the lower regions of the tubes having openings for introduction of the hot gas into the contents of the kettle.
- the number and size of the tubes is preferably such as to increase the surface area of the tubes available for heat exchange between the hot gas in the tubes and the material to be calcined by at least twice, and preferably three or four times, compared with that available in a conventional kettle.
- FIG. 1 is a diagrammatic vertical section through a calcining kettle according to a first preferred embodiment of the invention, containing gypsum;
- FIG. 2 is a diagrammatic vertical section through a calcining kettle according to a second preferred embodiment of the invention, containing gypsum;
- FIG. 3 is a diagrammatic representation of an alternative arrangement of combustion chamber and dip tubes for use in a kettle of the type shown in FIG. 1, with some of the dip tubes not shown.
- the kettle shown in FIG. 1 comprises an externally heated steel vessel 10 surrounded by a jacket 12.
- the space between the vessel 10 and the jacket 12 is supplied, from a source not shown in the drawings, with hot fluid such as hot gaseous combustion products.
- This fluid is also carried by cross tubes 14 through the vessel, which is provided with a stirrer 16.
- the upper wall or lid of the vessel is provided with an inlet 18 for powdered gypsum, and a vent 20 for exhaust gases.
- An outlet 22 for calcined gypsum is provided in the upper part of the vessel side wall enabling the kettle to operate continuously. This outlet is protected by a channel 24.
- Direct heat and fluidisation is provided by hot gas from a combustion chamber 26 mounted above the top wall or lid of the kettle.
- the combustion chamber 26 has a fuel inlet 28 and an air inlet 30.
- the fuel/air mixture is burnt in the combustion chamber 26, and passes into the kettle through a refractory lined tube 32 which extends just below the level 34 of gypsum in the kettle.
- the tube 32 opens into a plurality of dip tubes 36.
- the arrangement shown in FIG. 1 finds particular application when the fuel employed is oil. If the fuel employed is gas, the combustion chamber need not be lined with refractory material.
- the burner may be situated anywhere within this chamber.
- the dip tubes 36 are restrained against excessive movement by a frame 38 extending between the tubes. Preferably, this frame allows the tubes a little movement.
- FIG. 2 is a so-called conical kettle. It comprises a kettle 60, the lower portion of which has a generally conical shape and the bottom wall of which is provided with an upright cone 62 of heat resistant material which extends into the interior of the kettle.
- the kettle has a gypsum inlet 64 and an exhaust gas vent 66 in it upper wall, and an outlet 68 for calcined gypsum in its side wall, protected by a channel 70.
- the cone is absent from the bottom wall of the kettle 60, which is thus flat.
- Direct heat and fluidising is provided by hot gas from a combustion chamber 72 substantially within the upper portion of the interior of kettle 60.
- the combustion chamber 72 extends below the level 74 of the gypsum in the kettle.
- the combustion chamber has a fuel inlet 76 and an air inlet 78.
- the fuel/air mixture is burnt in the combustion chamber 72, and the hot gas produced leaves the combustion chamber through dip tubes 80, opening from the lower wall of the combustion chamber.
- the tubes are restrained against excessive movement by a framework 82 at their lower ends.
- the outer dip tubes are longer than the inner dip tubes to ensure efficient fluidisation of gypsum in the lowest region of the kettle. Since an increase in dip tube length increases the back pressure in the dip tube, the outer dip tubes are advantageously wider than the inner dip tubes to compensate.
- the plurality of dip tubes comprises 16 large (for example 4 inch (10 cm) diameter) dip tubes arranged in a ring around the outer edge of the combustion chamber 72, a first inner ring of 16 slightly smaller (for example 3 inch (7.5 cm) diameter) dip tubes, second and third inner rings of 12 and 8 small (for example 2 inch (5 cm) diameter) dip tubes and a central 3 inch (7.5 cm) diameter dip tube.
- the lengths of the dip tubes 80 are such that they end substantially the same distance above the upright cone on the bottom wall of the kettle 60.
- the dip tubes are of substantially the same length as each other, and preferably end between about 5 cm and 15 cm above the bottom wall of the kettle.
- FIG. 3 shows an alternative arrangement of combustion chamber 84 and dip tubes 86 for use in a kettle of the type shown in FIG. 1 embodying the invention. Some of the dip tubes 86 are not shown for clarity.
- the lower portion 88 of the combustion chamber 84 is in the form of an inverted frustocone.
- the dip tubes 86 open from the inclined face of the frustoconical lower portion 88 of the combustion chamber through openings 90, and extend downwardly into the kettle. Combustion takes place in the combustion chamber 84, and the hot gas generated passes out of the combustion chamber and into the gypsum in the kettle through the dip tubes 86.
- the hot gas passing down the dip tubes heats the surrounding gypsum by heat exchange through the dip tube walls.
- the rate of heat exchange can be increased by provision of internal or external fins on the dip tubes.
- the rate of heat exchange through the walls of the plurality of dip tubes is greater than is the case with a single dip tube, and so, for a given heat input to the dip tubes, the temperature of the gas entering the gypsum from the open lower ends of the dip tubes is lower. This results in a lower level of insoluble anhydrite formation.
- the temperature of the gas entering the gypsum is preferably about 700° C. to 800° C., but may be as low as 600° C. or 500° C.
- the number of tubes employed can vary, and some or all of the tubes may be provided with adjustable restrictions to control gas passage through them, enabling the heating and fluidisation of the bed to be controlled. Constraints on the size and number of tubes are the requirement that each tube be surrounded by gypsum and that the pressure drop across the tubes is not excessive.
- the gas entering the gypsum may be at the following temperatures:
- the average gas temperature, weighted for relative flow rate through the tubes, is 758° C. This compares with 1046° C. for a plain 44 inch (110 cm) diameter tube or 934° C. for a 44 inch (110 cm) diameter tube with 30 internal fins each 3 inch by 3/8 inch (7.5 cm by 1 cm).
- Heat transfer through the dip tube walls is improved.
- the total heat transfer is about 3.8 million Btu/hr, compared with less than 2 million Btu/hr for the 44 inch (110 cm) tube with the internal fins described above.
- the present invention provides a method and apparatus for calcining of gypsum in which lower temperature gases are in contact with the gypsum than has been possible before. This reduces the formation of insoluble anhydrite, and gives gypsum plaster of improved quality.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Meat, Egg Or Seafood Products (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Control And Other Processes For Unpacking Of Materials (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Inorganic Insulating Materials (AREA)
- Diaphragms For Electromechanical Transducers (AREA)
- Telephone Function (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
- Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Treatment Of Sludge (AREA)
- Crucibles And Fluidized-Bed Furnaces (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8625964 | 1986-10-30 | ||
GB868625964A GB8625964D0 (en) | 1986-10-30 | 1986-10-30 | Calcination apparatus |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US07115468 Continuation | 1987-10-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
US4915623A true US4915623A (en) | 1990-04-10 |
Family
ID=10606544
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US07/317,179 Expired - Lifetime US4915623A (en) | 1986-10-30 | 1989-02-28 | Calcination apparatus |
Country Status (9)
Country | Link |
---|---|
US (1) | US4915623A (de) |
EP (1) | EP0282674B1 (de) |
AT (1) | ATE66442T1 (de) |
AU (1) | AU604510B2 (de) |
DE (1) | DE3772377D1 (de) |
DK (1) | DK171273B1 (de) |
ES (1) | ES2024520B3 (de) |
GB (2) | GB8625964D0 (de) |
GR (1) | GR3002680T3 (de) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5580002A (en) * | 1993-08-27 | 1996-12-03 | Bpb Industries Public Limited Company | Method and apparatus for heating and grinding materials |
US5743954A (en) * | 1995-02-02 | 1998-04-28 | United States Gypsum Company | Method for continuous refractoryless calcining of gypsum |
US5743728A (en) * | 1995-08-15 | 1998-04-28 | Usg Corporation | Method and system for multi-stage calcining of gypsum to produce an anhydrite product |
US20050083173A1 (en) * | 2003-10-20 | 2005-04-21 | Konupek Ingrid H. | Locking remote control |
US20050190645A1 (en) * | 2004-02-27 | 2005-09-01 | Bolind Michael L. | Swinging agitator for a gypsum calcining apparatus and the like |
US20050188897A1 (en) * | 2004-02-27 | 2005-09-01 | Bolind Michael L. | High efficiency refractoryless kettle |
US20060274604A1 (en) * | 2004-02-27 | 2006-12-07 | Bolind Michael L | Swinging agitator for a gypsum calcining apparatus and the like |
JP2016155725A (ja) * | 2015-02-25 | 2016-09-01 | 吉野石膏株式会社 | 石膏焼成炉及び石膏焼成方法 |
WO2016136485A1 (ja) * | 2015-02-25 | 2016-09-01 | 吉野石膏株式会社 | 石膏焼成装置及び石膏焼成方法 |
JP2016155726A (ja) * | 2015-02-25 | 2016-09-01 | 吉野石膏株式会社 | 石膏焼成炉及び石膏焼成方法 |
WO2018030077A1 (ja) * | 2016-08-10 | 2018-02-15 | 吉野石膏株式会社 | 石膏処理装置及び石膏処理方法 |
US20190308906A1 (en) * | 2018-04-10 | 2019-10-10 | Tru-Flow Systems, Inc. | Calcining kettle, calcining system, and method |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2345135B1 (es) * | 2007-07-17 | 2011-07-18 | Fundacion Circe- Centro De Investigacion De Recursos Y Consumos Energeticos | Dispositivo ciclonico para calcinacion y procedimiento de separacion de co2 usando dicho dispositivo. |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1234240A (en) * | 1917-02-13 | 1917-07-24 | Carlton Geist | Fluid-fuel furnace for heating castings. |
US2464304A (en) * | 1944-08-10 | 1949-03-15 | Gottlieb Steven | Method of and shaft kiln for burning, calcining, or sintering, granulated or briquetted materials |
US4529374A (en) * | 1981-10-06 | 1985-07-16 | The British Petroleum Company P.L.C. | Gas particulate solid system |
US4576573A (en) * | 1982-12-29 | 1986-03-18 | Basf Aktiengesellschaft | Heating a fixed-bed charge in a tube reactor, and an arrangement for carrying out the method |
US4615867A (en) * | 1983-05-02 | 1986-10-07 | K. Systeme S.A.R.L. | Apparatus for cooking, dehydration and sterilization-drying of organic wastes |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL285104A (de) * | 1961-11-13 | |||
DE1558080B1 (de) * | 1967-03-23 | 1970-02-12 | Schilde Ag | Gipskocher mit Heissgaseinblasung |
GB1488665A (en) * | 1973-11-27 | 1977-10-12 | Bpb Industries Ltd | Calcining calcium sulphate dihydrate |
NL185896C (nl) * | 1979-01-08 | 1990-08-16 | Bpb Industries Ltd | Inrichting voor het met warmte behandelen van een korrelvormig materiaal. |
US4238238A (en) * | 1979-08-15 | 1980-12-09 | United States Gypsum Company | Calcining kettle having means for returning stack exhaust gas to calcining mixture |
GB2185419B (en) * | 1986-01-07 | 1990-04-18 | Bpb Industries Plc | Improvements in calcination apparatus |
-
1986
- 1986-10-30 GB GB868625964A patent/GB8625964D0/en active Pending
-
1987
- 1987-10-26 ES ES87309432T patent/ES2024520B3/es not_active Expired - Lifetime
- 1987-10-26 DE DE8787309432T patent/DE3772377D1/de not_active Expired - Lifetime
- 1987-10-26 AT AT87309432T patent/ATE66442T1/de not_active IP Right Cessation
- 1987-10-26 EP EP87309432A patent/EP0282674B1/de not_active Expired - Lifetime
- 1987-10-29 AU AU80486/87A patent/AU604510B2/en not_active Expired
- 1987-10-30 DK DK570087A patent/DK171273B1/da not_active IP Right Cessation
- 1987-10-30 GB GB08725491A patent/GB2198428A/en not_active Withdrawn
-
1989
- 1989-02-28 US US07/317,179 patent/US4915623A/en not_active Expired - Lifetime
-
1991
- 1991-09-10 GR GR91401291T patent/GR3002680T3/el unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1234240A (en) * | 1917-02-13 | 1917-07-24 | Carlton Geist | Fluid-fuel furnace for heating castings. |
US2464304A (en) * | 1944-08-10 | 1949-03-15 | Gottlieb Steven | Method of and shaft kiln for burning, calcining, or sintering, granulated or briquetted materials |
US4529374A (en) * | 1981-10-06 | 1985-07-16 | The British Petroleum Company P.L.C. | Gas particulate solid system |
US4576573A (en) * | 1982-12-29 | 1986-03-18 | Basf Aktiengesellschaft | Heating a fixed-bed charge in a tube reactor, and an arrangement for carrying out the method |
US4615867A (en) * | 1983-05-02 | 1986-10-07 | K. Systeme S.A.R.L. | Apparatus for cooking, dehydration and sterilization-drying of organic wastes |
Cited By (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5580002A (en) * | 1993-08-27 | 1996-12-03 | Bpb Industries Public Limited Company | Method and apparatus for heating and grinding materials |
US5743954A (en) * | 1995-02-02 | 1998-04-28 | United States Gypsum Company | Method for continuous refractoryless calcining of gypsum |
US5927968A (en) * | 1995-02-02 | 1999-07-27 | United States Gypsum Company | Apparatus for continuous refractoryless calcining of gypsum |
US5743728A (en) * | 1995-08-15 | 1998-04-28 | Usg Corporation | Method and system for multi-stage calcining of gypsum to produce an anhydrite product |
US5954497A (en) * | 1995-08-15 | 1999-09-21 | Usg Corporation | Method for multi-stage calcining of gypsum to produce an anhydrite product |
US20050083173A1 (en) * | 2003-10-20 | 2005-04-21 | Konupek Ingrid H. | Locking remote control |
US20050190645A1 (en) * | 2004-02-27 | 2005-09-01 | Bolind Michael L. | Swinging agitator for a gypsum calcining apparatus and the like |
US20050188897A1 (en) * | 2004-02-27 | 2005-09-01 | Bolind Michael L. | High efficiency refractoryless kettle |
US7121713B2 (en) * | 2004-02-27 | 2006-10-17 | United States Gypsum Company | Swinging agitator for a gypsum calcining apparatus and the like |
US20060274604A1 (en) * | 2004-02-27 | 2006-12-07 | Bolind Michael L | Swinging agitator for a gypsum calcining apparatus and the like |
US7175426B2 (en) | 2004-02-27 | 2007-02-13 | United States Gypsum Company | High efficiency refractoryless kettle |
US7434980B2 (en) | 2004-02-27 | 2008-10-14 | United States Gypsum Company | Swinging agitator for a gypsum calcining apparatus and the like |
JP2016155726A (ja) * | 2015-02-25 | 2016-09-01 | 吉野石膏株式会社 | 石膏焼成炉及び石膏焼成方法 |
AU2016225385B2 (en) * | 2015-02-25 | 2019-12-12 | Yoshino Gypsum Co., Ltd. | Apparatus and method for calcination of gypsum |
JP2016155725A (ja) * | 2015-02-25 | 2016-09-01 | 吉野石膏株式会社 | 石膏焼成炉及び石膏焼成方法 |
CN107406319A (zh) * | 2015-02-25 | 2017-11-28 | 吉野石膏株式会社 | 石膏煅烧装置及石膏煅烧方法 |
US20180036697A1 (en) * | 2015-02-25 | 2018-02-08 | Yoshino Gypsum Co., Ltd. | Apparatus and method for calcination of gypsum |
WO2016136485A1 (ja) * | 2015-02-25 | 2016-09-01 | 吉野石膏株式会社 | 石膏焼成装置及び石膏焼成方法 |
EP3263536A4 (de) * | 2015-02-25 | 2018-10-24 | Yoshino Gypsum Co., Ltd. | Vorrichtung und verfahren zur kalzinierung von gips |
CN107406319B (zh) * | 2015-02-25 | 2020-06-12 | 吉野石膏株式会社 | 石膏煅烧装置及石膏煅烧方法 |
US10350564B2 (en) | 2015-02-25 | 2019-07-16 | Yoshino Gypsum Co., Ltd. | Apparatus and method for calcination of gypsum |
RU2695722C2 (ru) * | 2015-02-25 | 2019-07-25 | Йосино Джипсум Ко., Лтд. | Устройство и способ для кальцинации гипса |
WO2018030077A1 (ja) * | 2016-08-10 | 2018-02-15 | 吉野石膏株式会社 | 石膏処理装置及び石膏処理方法 |
KR20190039062A (ko) * | 2016-08-10 | 2019-04-10 | 요시노 셋고 가부시키가이샤 | 석고 처리 장치 및 석고 처리 방법 |
RU2725472C1 (ru) * | 2016-08-10 | 2020-07-02 | Йосино Джипсум Ко., Лтд. | Устройство и способ обработки гипса |
KR102364773B1 (ko) | 2016-08-10 | 2022-02-18 | 요시노 셋고 가부시키가이샤 | 석고 처리 장치 및 석고 처리 방법 |
US11512019B2 (en) | 2016-08-10 | 2022-11-29 | Yoshino Gypsum Co., Ltd. | Apparatus and method for treating gypsum |
US20190308906A1 (en) * | 2018-04-10 | 2019-10-10 | Tru-Flow Systems, Inc. | Calcining kettle, calcining system, and method |
US11046611B2 (en) * | 2018-04-10 | 2021-06-29 | Tru-Flow Systems, Inc. | Calcining kettle, calcining system, and method |
Also Published As
Publication number | Publication date |
---|---|
ATE66442T1 (de) | 1991-09-15 |
AU604510B2 (en) | 1990-12-20 |
ES2024520B3 (es) | 1992-03-01 |
EP0282674A3 (en) | 1988-12-28 |
GB8725491D0 (en) | 1987-12-02 |
EP0282674A2 (de) | 1988-09-21 |
EP0282674B1 (de) | 1991-08-21 |
GB8625964D0 (en) | 1986-12-03 |
DK171273B1 (da) | 1996-08-19 |
AU8048687A (en) | 1988-05-05 |
GR3002680T3 (en) | 1993-01-25 |
DK570087A (da) | 1988-05-01 |
GB2198428A (en) | 1988-06-15 |
DK570087D0 (da) | 1987-10-30 |
DE3772377D1 (de) | 1991-09-26 |
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